WO2006045407A2 - Compositions amines-epoxy a proprietes de resistance chimique elevee - Google Patents

Compositions amines-epoxy a proprietes de resistance chimique elevee Download PDF

Info

Publication number
WO2006045407A2
WO2006045407A2 PCT/EP2005/010721 EP2005010721W WO2006045407A2 WO 2006045407 A2 WO2006045407 A2 WO 2006045407A2 EP 2005010721 W EP2005010721 W EP 2005010721W WO 2006045407 A2 WO2006045407 A2 WO 2006045407A2
Authority
WO
WIPO (PCT)
Prior art keywords
composition
amines
epoxy
glycidyl ether
hardener
Prior art date
Application number
PCT/EP2005/010721
Other languages
English (en)
Other versions
WO2006045407A3 (fr
Inventor
Jan Dirk Bossaerts
Marc Jozef Rans
Original Assignee
Hexion Specialty Chemicals Research Belgium S.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hexion Specialty Chemicals Research Belgium S.A. filed Critical Hexion Specialty Chemicals Research Belgium S.A.
Priority to EP05795615A priority Critical patent/EP1809683A2/fr
Publication of WO2006045407A2 publication Critical patent/WO2006045407A2/fr
Publication of WO2006045407A3 publication Critical patent/WO2006045407A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/36—Epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines

Definitions

  • the invention relates to epoxy resin curable compositions, more particularly to epoxy curable compositions, comprising aromatic halogenated glycidyl ether resins to be cured with aliphatic amines, which are intended for the impregnation of fibers applicable to the manufacturing of composite structures, laminates, coatings, flooring and putties applications and which show a particularly high resistance to aggressive chemicals in which they are immersed.
  • the aromatic amines and more particularly the diamines were introduced at an early stage into the epoxy technology. They are recognized in the art as the cured networks that provide improved heat and chemical resistance over that attained with the aliphatic amines.
  • the aromatic amines generally react slowly with glycidyl ethers and usually require heat to achieve a fully cured network and also the maximum properties.
  • the most commonly used aromatic amine is from far 4,4'- methylenedianiline (MDA) which is a solid (or semi-solid) and therefore is not always easy to formulate into epoxy resin compositions.
  • MDA far 4,4'- methylenedianiline
  • Proposed solutions to these problems were directed to the formulation of blends with other aromatic amines or to add diluents, US 4,229,563 which discloses curing agents for epoxy resins derived from hydroxy or dihydroxy benzoic acid reacted with aliphatic polyamines.
  • the chemical resistance of the cured films based thereof could not meet those of their obtained by curing with MDA based formulations. Therefore the need for an adequate alternative for the aromatic amine cured epoxy systems is still a current issue.
  • An object of this invention is to provide an epoxy resin curable composition which is curable at ambient temperature and which provides a performance superior or equal to that on of the aromatic amine/epoxy resin cured compositions.
  • the present invention provides compositions that fulfill this object.
  • the present invention relates to a curable or polymerizable epoxy resin composition
  • an epoxy resin part (a) which comprises a combination of: (a,i) at least an aromatic halogenated glycidyl ether resin, (a,ii) a non halogenated glycidyl ether resin and
  • a,iii optionally a reactive diluent or/and a solvent, and a harderner part (b) comprising aliphatic, cyclo- aliphatic, aromatic amines, and optionally a diluent and/or a solvent .
  • the aromatic halogenated glycidyl ether resins (a,i) used in this invention are derived from halogenated phenol reacted with a keto compound and subsequently with halohydrine and oligomers thereof.
  • the most preferred halogen atoms are bromine and chlorine, the most preferred keto compounds are acetone and formaldehyde.
  • Commercially available halogenated resins are for example EPON 1163, EPIKOTE 5123, EPIKOTE 5119 and EPIKOTE 5112 (EPON/EPIKOTE are Resolution Performance Products Trademarks) or any other glycidyl ether of tetra-bromo- Bis-Phenol derivatives which contains more than 10 weight% of brome on resinous material .
  • the non halogenated epoxy resins (a,ii) used in the composition of this invention is a liquid or medium molecular weight solid resin or a mixture thereof.
  • the epoxy resins used could also contain a generally known additive known in the art to improve flexibility and/or the adhesion capacity to the various substrates .
  • the preferred non halogenated epoxy resins (a,ii) for the composition of this invention are the diglycidyl ether of Bisphenol A, and/or Bisphenol F and/or polyglycidyl ethers of phenol/cresol-formaldehyde novolacs, and the like.
  • Examples of such resins are: EPIKOTE 828, EPIKOTE
  • the diluents could be non reactive such as for example benzyl alcohol or nonyl-phenol, or reactive such as a glycidyl ether derivative, a glycidyl ester derivative such as for example CARDURA ElO (CARDURA is a Resolution Performance Products Trademark) or hexadioldiglycidylether.
  • the solvent could be any solvent in which the above resins are soluble and could be used up to 80 weight% on resins (i) and (ii) and diluent.
  • the hardener part (b) of this invention consist of an aliphatic amine such as diethylenetriamine (DETA) , triethylenetetramine (TETA) , teraethylenepentamine (TEPA) , isophorone diamine (IPD) , para-aminocyclohexane methylene (PACM) , diamino cyclohexane (DCH) , meta-Xylene diamine (mXDA) , 4, 4 ' -Diamino 3, 3 ' -dimethyl diCyclohexyl methane (DDCM) and adducts of aliphatic amines such as based on DETA,TETA,TEPA, IPD, PACM,DCH, mXDA, DDCM and the like.
  • DETA diethylenetriamine
  • TETA triethylenetetramine
  • TEPA teraethylenepentamine
  • IPD isophorone diamine
  • PAM para-aminocyclohe
  • amines containing a cyclic structure such as IPD, PACM, mXDA and DCH or a mixture thereof.
  • aromatic amines such as MDA could be used as well even if they are not preferred for the reason discussed above in the introduction.
  • the most preferred non reactive diluent is benzyl alcohol .
  • composition according to this invention could be formulated into a paint to protect metal parts, or for putty systems, or thin laminates such as the one used in tank lamination repair systems.
  • said above composition is that it could be used in making composite material with glass, carbon or natural fibre by the technology known in the art .
  • Gelation time the time in minutes required for a mixture of resin and curing agent, maintained at a fixed temperature, to reach the stage in the process of hardening at which the resistance to the movement of a slowly reciprocating plunger immersed in the mixture reaches a specific value.
  • Method summary Heat the individual components to such a temperature that, after mixing, the final temperature of the mixture will be 0 to 2 0 C below the test temperature.
  • a 150 g mixture is prepared in a tin.
  • a lOOg of the mixture is poured into the aluminum container.
  • Apparatus Gel timer, according to BS 2782: Part 8, Method 835C, with disposable glass disk plungers. (Tecam Gel Timer, model GT3) .
  • Aluminum container ID 40 to 47 mm, depth not less than 75 mm and wall thickness 0.35 to 0.51 mm.
  • Dynamic Viscosity of the mixture (resin + curing agent) in mPa.s is measured according to ASTM D 2393. The temperature is 25°C.
  • the apparatus used is a Brookfield DVII, with a spindle LV II (for low viscosities) .
  • Wetting time the time in minutes, needed for 2 grams of the mixture to penetrate a glass fiber mat, until the surface goes from a glossy to a matt appearance (the mixture is absorbed by the glass mat) .
  • Spot size diameter of the spot in mm, after curing at 25 0 C of the 2 grams of the mixture.
  • Glass mat a chopped strand mat of size-coated chopped strands, with a thickness of 450 g/m 2 .
  • Test specimens of the dimensions (80x10x4) mm were cut from the casting sheets by a diamond saw. Moulds used for the castings consisted of 2 steel plates with a 4 mm frame in between. The castings were cured in the mould.
  • the relative rate of absorption of the immersed test pieces was measured according to ASTM D570- 98 Standard Test Method.
  • the test media were demineralized water, toluene and aqueous HCl 10%.
  • Epoxy resin part The epoxy resin(s) is (are put in a glass reactor with heating jacket. The temperature is raised to 90 0 C and stirred for 2 hours.
  • Resin 1 EPIKOTE 828L VE (37.5 weight%) , EPIKOTE 1163 (37.5 w%) CARDURA ElO (25w%) .
  • Resin 2 EPIKOTE 862 (42.5 weight%) , EPIKOTE 1163 (42.5 w%) Heloxy 66 (15w%) .
  • Resin 3 EPIKOTE 862 (37.5 weight%) , EPIKOTE 1163 (37.5 w%) Heloxy 66 (25w%) .
  • Comparative resin a EPIKOTE 862 (42.5 weight%),EPIKOTE 828L VE (42.5 w%)Heloxy 66 (15w%) .
  • Comparative resin b EPIKOTE 154 (50 weight%) ,Heloxy 48(50 w%) .
  • Comparative resin c EPIKOTE 816.
  • Hardener part The hardener parts are mixed in a glass reactor at ambient temperature for 10 minutes. Note for the comparative hardener and the temperature in the glass reactor was 9O 0 C and the mixing time 2 hours.
  • Hardener 3 mXDA/ IPD/ DCH 90/5/5 (total 80 w%) ,BA(20 w%)
  • Hardener 4 PACM 50w% IPD 45w% DCH 5w%
  • Hardener 5 PACM 40w% IPD 36w% DCH 4w% BA 20w% Hardener 6 : mXDA 50w% DCH 45w% IPD 5w%
  • Comparative hardener a DETDA/salicylic acid (90/10)
  • Comparative hardener b EPIKURE 161 (MDA based)
  • Formulation part The properties of the formulation mixture, like reactivity, fiber wetting are measured on freshly prepared mixtures.
  • the epoxy resin part and the hardener part are stored in a conditioned room at 23 0 C, weighted in an open tin and mixed with a large spatula at this temperature.
  • Table 1 formulations according to the invention

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne le domaine des compositions de résine époxy durcissables, et plus précisément une composition époxy durcissable à résines de glycidyléther halogénées durcies par des amines, pour l'imprégnation de fibres applicables ou pour l'élaboration de structures composites, de laminations, de revêtements, de revêtements de sol et de mastics, présentant une résistance particulièrement forte aux produits chimiques agressifs.
PCT/EP2005/010721 2004-10-21 2005-10-05 Compositions amines-epoxy a proprietes de resistance chimique elevee WO2006045407A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05795615A EP1809683A2 (fr) 2004-10-21 2005-10-05 Compositions de résines epoxy-amines ayant une haute résistance chimique

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP04077902A EP1650247A1 (fr) 2004-10-21 2004-10-21 Compositions de résines Epoxy-amines ayant une haute résistance chimique
EP04077902.7 2004-10-21

Publications (2)

Publication Number Publication Date
WO2006045407A2 true WO2006045407A2 (fr) 2006-05-04
WO2006045407A3 WO2006045407A3 (fr) 2007-08-16

Family

ID=34928588

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2005/010721 WO2006045407A2 (fr) 2004-10-21 2005-10-05 Compositions amines-epoxy a proprietes de resistance chimique elevee

Country Status (3)

Country Link
US (1) US20070244269A1 (fr)
EP (2) EP1650247A1 (fr)
WO (1) WO2006045407A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016098130A1 (fr) 2014-12-16 2016-06-23 Council Of Scientific & Industrial Research Composites de novolaque époxydique
WO2024079077A1 (fr) 2022-10-11 2024-04-18 Akzo Nobel Coatings International B.V. Composition de revêtement durcissant à basse température

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20091980A1 (it) * 2009-11-12 2011-05-13 Imast S C A R L Polimeri rinforzati con fibre, composizioni polimeriche a base epossidica e loro impiego
US9548252B2 (en) * 2013-11-19 2017-01-17 Raytheon Company Reworkable epoxy resin and curative blend for low thermal expansion applications
EP3109935B1 (fr) * 2015-06-26 2019-11-27 IMEC vzw Élément de couplage pour coupleur hybride différentiel

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3523037A (en) * 1967-06-12 1970-08-04 Ibm Epoxy resin composition containing brominated polyglycidyl ether of bisphenol a and a polyglycidyl ether of tetrakis(hydroxyphenyl) ethane
US4229563A (en) * 1979-08-03 1980-10-21 Ameron, Inc. Aromatic amidoamines
JPS59136319A (ja) * 1983-01-25 1984-08-04 Nissan Chem Ind Ltd 難燃性基板エポキシ樹脂組成物
EP0303225A2 (fr) * 1987-08-10 1989-02-15 Kashima Industries, Co. Film de résine époxy recouvert d'une feuille de métal et circuit imprimé flexible
US5405931A (en) * 1991-04-03 1995-04-11 The Dow Chemical Company Epoxy resin compositions for use in electrical laminates
US6054509A (en) * 1997-08-28 2000-04-25 Shin-Etsu Chemical Co., Ltd. Adhesive of epoxy resin, nitrile rubbers and curing agent

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5962602A (en) * 1995-08-18 1999-10-05 Sika Corporation Usa Ultra-low viscosity epoxy sealer/healer
JPH09109447A (ja) * 1995-10-13 1997-04-28 Tec Corp 画像形成装置

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3523037A (en) * 1967-06-12 1970-08-04 Ibm Epoxy resin composition containing brominated polyglycidyl ether of bisphenol a and a polyglycidyl ether of tetrakis(hydroxyphenyl) ethane
US4229563A (en) * 1979-08-03 1980-10-21 Ameron, Inc. Aromatic amidoamines
JPS59136319A (ja) * 1983-01-25 1984-08-04 Nissan Chem Ind Ltd 難燃性基板エポキシ樹脂組成物
EP0303225A2 (fr) * 1987-08-10 1989-02-15 Kashima Industries, Co. Film de résine époxy recouvert d'une feuille de métal et circuit imprimé flexible
US5405931A (en) * 1991-04-03 1995-04-11 The Dow Chemical Company Epoxy resin compositions for use in electrical laminates
US6054509A (en) * 1997-08-28 2000-04-25 Shin-Etsu Chemical Co., Ltd. Adhesive of epoxy resin, nitrile rubbers and curing agent

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE CA [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 12 May 1984 (1984-05-12), TAMURA, TORU ET AL: "Protective coating on zinc oxide type varistors" XP002322205 retrieved from STN Database accession no. 83:20681 & JP 49 109447 A2 (MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD., JAPAN) 17 October 1974 (1974-10-17) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016098130A1 (fr) 2014-12-16 2016-06-23 Council Of Scientific & Industrial Research Composites de novolaque époxydique
WO2024079077A1 (fr) 2022-10-11 2024-04-18 Akzo Nobel Coatings International B.V. Composition de revêtement durcissant à basse température

Also Published As

Publication number Publication date
US20070244269A1 (en) 2007-10-18
WO2006045407A3 (fr) 2007-08-16
EP1650247A1 (fr) 2006-04-26
EP1809683A2 (fr) 2007-07-25

Similar Documents

Publication Publication Date Title
EP3052541B1 (fr) Compositions liquides d'un agent de durcissement pour époxy
US9074041B2 (en) Curable epoxy resin compositions and composites made therefrom
TWI752973B (zh) 作為快速環氧固化劑之室溫離子液體
KR102205915B1 (ko) 섬유-매트릭스 반마감 생성물용 에폭시드 수지 조성물
CN107542226B (zh) 由蒸压加气混凝土（aac）制成的加筋建筑砌块
EP2157113B1 (fr) Éthylènediamines aminopropylés d'alkylat et utilisations associées
KR20100018471A (ko) 벤질화 아미노프로필화된 에틸렌디아민 및 이의 용도
JP7569620B2 (ja) エポキシ配合物用のモノアルキル化ジアミン：エポキシ系用の新規硬化剤
JP7242694B2 (ja) エポキシ配合物のための脂環式アミン：エポキシ系のための新規な硬化剤
US20070244269A1 (en) Amines-epoxy compositions with high chemical resistance properties
JP5801824B2 (ja) ジビニルアレーンジオキシド樹脂組成物
EP1302495B1 (fr) Composition de resine epoxyde et materiau composite renforce par des fibres constituees de la composition de resine epoxyde
US5880228A (en) Hardeners for epoxy resin systems, which are formed from epoxy, monohydroxy aromatic, and amine adducts
JP5762402B2 (ja) 耐薬品性の金型および治工具の製造方法
US20230257511A1 (en) Epoxy-amine adduct
WO2023174747A1 (fr) Nouvelle composition de résine époxy destinée à être utilisée en tant qu'adhésif structural
CN117794975A (zh) 胺组合物、由该胺组合物和环氧树脂制成的环氧体系和该环氧体系的用途

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BW BY BZ CA CH CN CO CR CU CZ DK DM DZ EC EE EG ES FI GB GD GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV LY MD MG MK MN MW MX MZ NA NG NO NZ OM PG PH PL PT RO RU SC SD SG SK SL SM SY TJ TM TN TR TT TZ UG US UZ VC VN YU ZA ZM

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GM KE LS MW MZ NA SD SZ TZ UG ZM ZW AM AZ BY KG MD RU TJ TM AT BE BG CH CY DE DK EE ES FI FR GB GR HU IE IS IT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW MR NE SN TD TG

WWE Wipo information: entry into national phase

Ref document number: 2005795615

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWP Wipo information: published in national office

Ref document number: 2005795615

Country of ref document: EP